Multilayer film for decorative moldnig, polyurethane resin, and method for producing decorative molded body

ABSTRACT

A multilayer film includes a protective layer, a color layer and an adhesive layer, with a molding film disposed between either of the adjoining pairs of layers or on an opposite surface of the protective layer to the color layer, wherein the protective layer contains a polyurethane resin (U) formed at least from an active hydrogen component (A) and an organic isocyanate component (B) and having a polycarbonate skeleton with an alicyclic hydrocarbon group and that conditions (1) and/or (2) are satisfied:
         (1): The polyurethane resin (U) is a polyurethane resin (U1) having an alkoxysilyl and/or a silanol group in a molecule,   (2): The protective layer contains a compound (X) having a glycidyl ether, and an alkoxysilyl and/or a silanol group, and the polyurethane resin (U) is a polyurethane resin (U2) that has an amino group, or a carboxyl group and/or a salt thereof.

TECHNICAL FIELD

This disclosure relates to a multilayer film for decorative molding usedwhen providing film decoration for decorable objects used in automobileparts, electrical appliances and the like, more specifically, amultilayer film for decorative molding which exhibits a goodmold-conformability to decorable objects, even those with deep-draws andother complicated shapes, during decorative molding, and scratch markresistance, and a polyurethane resin used therefor, as well as a methodof producing a decorative molded body.

BACKGROUND ART

Generally speaking, when it comes to a method to decorate moldedproducts such as automobile parts and electrical appliances, a techniquedesigned to decorate decorable objects by spray-coating multiple layerswith different functions such as an adhesive layer, color layer andprotective layer one by one to confer durability, esthetic design andthe like on them has been adopted. However, there is a problem with sucha technique in that, since spray-coating necessitates a baking step,there are more steps than otherwise is the case, the cost is high due tothe considerable energy and time involved in heating. To solve thisproblem, film-based decorating methods capable of decoratingthree-dimensional decorable objects, such as vacuum molding andair-pressure forming, have been studied in recent years.

Designed to cover the outermost surface of a molded product, theprotective layer of a multilayer film for decorative molding used in afilm-based decorating method plays an important role in the decorationof a molded product, and, as such, needs to possess durability (forinstance, anti-scratching properties (scratch resistance), weatherresistance, chemical resistance and water resistance).

In addition, when applying a film-based decorating method to automobileand other parts, mold-conformability during decorative molding isessential because of the large size and complex shape of moldedproducts. Namely, to decorate a molded product using a film-baseddecorating method, it is necessary that the whole surface from top tobottom be covered in one go even if the molded product is large in size.Similarly, when a complex shape is involved, the multilayer film fordecorative molding needs to fit the whole surface by deforming to theshape of every peak and trough.

The protective layer of a multilayer film for decorative molding needsparticularly to have scratch resistance and, as part of a multilayerfilm for decorative molding, mold-conformability during decorativemolding, and there are growing calls for those characteristics.

Further, application of a film-based decorating method to automobile andother parts is accompanied by a requirement for high productivity,namely the completion of a molding operation with only a few steps.

As a multilayer film for decorative molding, a moldable film featuring aprotective layer that mainly comprises an acrylic resin as described inJapanese Unexamined Patent Publication (Kokai) No. 2004-299223, OfficialGazette and Japanese Unexamined Patent Publication (Kokai) No.2003-212938, Official Gazette, for instance, has been proposed.

A moldable film that mainly comprises urethane resin and is designed tobe cured by heat curing alone as described in Japanese Unexamined PatentPublication (Kokai) No. 2010-260942, Official Gazette has also beenproposed.

The method described in Japanese Unexamined Patent Publication (Kokai)No. 2004-299223, Official Gazette and Japanese Unexamined PatentPublication (Kokai) No. 2003-212938, Official Gazette has a problem inthat its productivity is low because it needs to, after bonding amultilayer film for decorative molding to the decorable object, run anextra step of irradiating it with an energy ray using a UV lamp to curethe protective layer. The method described in Japanese Unexamined PatentPublication (Kokai) No. 2010-260942, Official Gazette also has a problemin that it cannot simultaneously achieve the scratch resistance of theprotective layer and its mold-conformability during decorative moldingdespite both being essential properties.

In light of such limitations, it could be helpful to provide ahigh-productivity multilayer film for decorative molding that features aprotective layer having both good stretchability, as suited forfilm-based decorative molding, and good scratch resistance.

SUMMARY

We provide the film configurations described in [1] to [19] below.

[1] A multilayer film for decorative molding which has a multilayerstructure wherein a protective layer, a color layer and an adhesivelayer are arranged in this order, with a molding film inserted betweeneither of the adjoining pairs of layers or placed on the surface of theprotective layer located on the opposite side to the color layer, andwhich is characterized in that its protective layer contains apolyurethane resin (U) formed at least from an active hydrogen component(A) and an organic isocyanate component (B) and having a polycarbonateskeleton with an alicyclic hydrocarbon group and that it satisfiescondition (1) and/or condition (2).

Condition (1): The polyurethane resin (U) is a polyurethane resin (U1)that has an alkoxysilyl group and/or a silanol group in a molecule.

Condition (2): The protective layer contains a compound (X) that has aglycidyl ether group, and an alkoxysilyl group and/or a silanol group,and the polyurethane resin (U) is a polyurethane resin (U2) that has anamino group, or a carboxyl group and/or a salt thereof.

[2] A multilayer film for decorative molding as described in [1] whereinthe active hydrogen component (A) contains a polycarbonate polyol (a1)having an alicyclic hydrocarbon group.

[3] A multilayer film for decorative molding as described in [2] whereinthe number average molecular weight of the polycarbonate polyol (a1) is500 to 5,000 and the mass fraction of the alicyclic hydrocarbon groupcontained in the polycarbonate polyol (a1) is 1 to 30 mass % relative tothe combined mass of the active hydrogen component (A) and the organicisocyanate component (B).

[4] A multilayer film for decorative molding as described in any of [1]to [3] wherein the combined mass fraction of the Si atoms attributed tothe alkoxysilyl group and/or the silanol group contained in thepolyurethane resin (U) and the Si atoms attributed to the alkoxysilylgroup and/or the silanol group contained in the compound (X) is 0.05 to2.0 mass % relative to the combined mass of the active hydrogencomponent (A) and the organic isocyanate component (B).

[5] A multilayer film for decorative molding as described in any of [1]to [4] wherein the organic isocyanate component (B) comprises analicyclic polyisocyanate (b1) with a carbon number of 6 to 18 and/or analiphatic polyisocyanate (b2) with a carbon number of 4 to 22.

[6] A multilayer film for decorative molding as described in any of [1]to [4] wherein the organic isocyanate component (B) comprises isophoronediisocyanate and/or 4,4-dicyclohexyl methane diisocyanate.

[7] A polyurethane resin used in a multilayer film for decorativemolding characterized in that it is formed at least from an activehydrogen component (A) and an organic isocyanate component (B) and thatit has a polycarbonate skeleton with an alicyclic hydrocarbon group andhas an alkoxysilyl group and/or a silanol group.

[8] A polyurethane resin as described in [7] wherein the active hydrogencomponent (A) contains a polycarbonate polyol (a1) having an alicyclichydrocarbon group.

[9] A polyurethane resin as described in [8] wherein the number averagemolecular weight of the polycarbonate polyol (a1) is 500 to 5,000 andthe mass fraction of the alicyclic hydrocarbon group contained in thepolycarbonate polyol (a1) is 1 to 30 mass % relative to the combinedmass of the active hydrogen component (A) and the organic isocyanatecomponent (B).

[10] A polyurethane resin as described in any of [7] to [9] wherein themass fraction of the Si atoms attributed to the alkoxysilyl group and/orthe silanol group contained in a polyurethane resin (U1) is 0.05 to 2.0mass % relative to the combined mass of the active hydrogen component(A) and the organic isocyanate component (B).

[11] A polyurethane resin as described in any of [7] to [10] wherein theorganic isocyanate component (B) comprises an alicyclic polyisocyanate(b1) with a carbon number of 6 to 18 and/or an aliphatic polyisocyanate(b2) with a carbon number of 4 to 22.

[12] A polyurethane resin as described in any of [7] to [10] wherein theorganic isocyanate component (B) comprises isophorone diisocyanateand/or 4,4-dicyclohexyl methane diisocyanate.

[13] A polyurethane resin composition which is formed at least from anactive hydrogen component (A) and an organic isocyanate component (B),has a polycarbonate skeleton with an alicyclic hydrocarbon group andcontains a polyurethane resin (U2) having an amino group, or a carboxylgroup and/or a salt thereof, and a compound (X) having a glycidyl ethergroup, and an alkoxysilyl group and/or a silanol group, and which ischaracterized in that it is used in a multilayer film for decorativemolding.

[14] A polyurethane resin composition as described in [13] wherein theactive hydrogen component (A) contains a polycarbonate polyol (a1)having an alicyclic hydrocarbon group.

[15] A polyurethane resin composition as described in [14] wherein thenumber average molecular weight of the polycarbonate polyol (a1) is 500to 5,000 and the mass fraction of the alicyclic hydrocarbon groupcontained in the polycarbonate polyol (a1) is 1 to 30 mass % relative tothe combined mass of the active hydrogen component (A) and the organicisocyanate component (B).

[16] A polyurethane resin composition as described in any of [13] to[15] wherein the mass fraction of the Si atoms attributed to thealkoxysilyl group and/or the silanol group contained in a compound (X)is 0.05 to 2.0 mass % relative to the combined mass of the activehydrogen component (A) and the organic isocyanate component (B).

[17] A polyurethane resin composition as described in any of [13] to[16] wherein the organic isocyanate component (B) comprises an alicyclicpolyisocyanate (b1) with a carbon number of 6 to 18 and/or an aliphaticpolyisocyanate (b2) with a carbon number of 4 to 22.

[18] A polyurethane resin composition as described in any of [13] to[16] wherein the organic isocyanate component (B) comprises isophoronediisocyanate and/or 4,4-dicyclohexyl methane diisocyanate.

[19] A method for producing a decorative molded body obtained by bondinga multilayer film for decorative molding onto a decorable object whichis characterized in that the multilayer film for decorative molding hasa multilayer structure wherein a protective layer, a color layer and anadhesive layer are arranged in this order, with a molding film insertedbetween either of the adjoining pairs of layers or placed on the surfaceof the protective layer located on the opposite side to the color layer,that the protective layer of the multilayer film for decorative moldingcontains a polyurethane resin (U) formed at least from an activehydrogen component (A) and an organic isocyanate component (B) andhaving a polycarbonate skeleton with an alicyclic hydrocarbon group, andthat the multilayer film for decorative molding satisfies condition (1)and/or condition (2).

Condition (1): The polyurethane resin (U) has an alkoxysilyl groupand/or a silanol group in a molecule.

Condition (2): The protective layer contains a compound (X) that has aglycidyl ether group, and an alkoxysilyl group and/or a silanol group,and the polyurethane resin (U) has a carboxyl group and/or a saltthereof.

Since the multilayer film for decorative molding is excellent inmold-conformability during decorative molding and, in addition, onlyneeds the heat generated during the molding process to have the curingof the protective layer sufficiently progress and be completed, its usemakes it possible to obtain a decorative molded body having highproductivity, as well as good mold-conformability during decorativemolding and durability (e.g. scratch resistance, weather resistance,chemical resistance and water resistance).

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic cross-sectional drawing illustrating a multilayerfilm for decorative molding relating to an example.

FIG. 2 is a schematic cross-sectional drawing illustrating a multilayerfilm for decorative molding relating to another example.

FIG. 3 is a schematic cross-sectional drawing illustrating a multilayerfilm for decorative molding relating to yet another example.

DETAILED DESCRIPTION Explanation of Numerical Symbols

-   -   1 Molding film    -   2 Protective layer    -   3 Color layer    -   4 Adhesive layer

A multilayer film for decorative molding which has a multilayerstructure wherein a protective layer, a color layer and an adhesivelayer are arranged in this order, with a molding film inserted betweeneither of the adjoining pairs of layers or placed on the surface of theprotective layer located on the opposite side to the color layer, whoseprotective layer contains a polyurethane resin (U) formed at least froman active hydrogen component (A) and an organic isocyanate component (B)and having a polycarbonate skeleton with an alicyclic hydrocarbon group,and which satisfies condition (1) (The polyurethane resin (U) is apolyurethane resin (U1) that has an alkoxysilyl group and/or a silanolgroup in a molecule). and/or condition (2) (The protective layercontains a compound (X) that has a glycidyl ether group, and analkoxysilyl group and/or a silanol group, and the polyurethane resin (U)is a polyurethane resin (U2) that has an amino group, or a carboxylgroup and/or a salt thereof) is suitable for providing a decorableobject with a surface decoration by placing its adhesive layer closelyover the surface of the decorable object and bonding them bythermoforming. The sequential order of the color layer and adhesivelayer can be any of the options (i) to (iii) listed below. In thisregard, the list shows the decorable object in brackets to clearlyillustrate the configurational aspects of the embodiments of the presentinvention despite the fact that it is not included in the multilayerfilm for a decorative molding.

(i) Molding film/protective layer/color layer/adhesive layer (/decorableobject)

(ii) Protective layer/molding film/color layer/adhesive layer(/decorable object)

(iii) Protective layer/color layer/molding film/adhesive layer(/decorable object)

If configurational option (i) is adopted, it is necessary to remove themolding film because of the need to expose the protective layer as theoutermost face after decorative molding. Hereinafter, the compositelayer comprising of the layers from the protective layer to the adhesivelayer in any of patterns (a) to (c) below to be formed over thedecorable object may be referred to as “decorative layer”.

(a) A composite layer (protective layer/color layer/adhesive layer) inthe case of adopting configuration (i) with the molding film removed

(b) A composite layer (protective layer/molding film/colorlayer/adhesive layer) in the case of adopting configuration (ii)

(c) A composite layer (protective layer/color layer/moldingfilm/adhesive layer) in the case of adopting configuration (iii)

Decorating a decorable object using such a multilayer film fordecorative molding makes it possible to reduce the number of stepsforming a decorative layer compared to a decorating method based onconventional spray-coating, which involves multi-stage steps, thusimproving the production efficiency of molded products having adecorative layer. This, in turn, makes it possible to lower the cost.

Since such a multilayer film for decorative molding features aprotective layer that satisfies condition (1) and/or condition (2) asspecified above, the heat generated during the molding process alone isenough to have the curing of its protective layer proceed, and thisincreases productivity by eliminating the need for a separate energy rayirradiation step. It also exhibits good scratch resistance and goodmold-conformability during decorative molding. The use of such amultilayer film for decorative molding, therefore, makes it possible toobtain a decorative molded body with good external appearance.

Molding Film

There are no specific limitations on the kind of film used as a moldingfilm, as long as it has a rupture elongation of 150% or more at 100° C.and is obtained by processing a thermoplastic resin, such as polyolefin,polyester, polyvinyl chloride, poly(meta-)acrylate, polyamide, polyesteramide, polyether, polystyrene, polyether ester and polycarbonate. Itdoes not matter whether it is an unstretched film, uniaxially stretchedfilm or biaxially stretched film.

It is preferable that the molding film of a multilayer film fordecorative molding not become detached from the adjoining layers duringhandling or decorative molding.

When the multilayer film for decorative molding takes configuration (i)above, it is necessary that, in addition to preventing the molding filmfrom being detached from the protective layer at the interface betweenthem during handling or decorative molding as described above, themolding film be peeled and removed after decorative molding iscompleted. In this case, therefore, it is preferable that, in additionto maintaining contact with the protective layer before and duringdecorative molding, the protective layer-side surface of the moldingfilm be releasable from the protective layer after decorative molding.Though these are mutually exclusive characteristics, it is possible toadjust them appropriately by combining a contact relaxing method and acontact tightening method as described below. Examples of a contactrelaxing method include the use of a composite film produced by applyinga layer made of a material with low affinity for the protective layer,such as polyolefin, to one side of the molding film (protectivelayer-side surface) by coextrusion or laminating and coating of themolding film with a mold releasing agent to obtain a composite film.Examples of a contact tightening method include the provision of acorona treatment on one side of the molding film (protective layer-sidesurface).

When the multilayer film for decorative molding takes configuration (ii)or (iii) above, the molding film is embedded in the decorative layer sothat there is no need for its two surfaces to have releasability withrespect to the adjoining layers, with the only requirement being closecontact. It therefore suffices to provide an adequate level of contactusing a method such as the surface coating of the molding film with anadhesive to turn it into a composite film or a surface modification ofthe molding film through corona treatment or the like.

It is preferable that the thickness of the molding film be 50 to 500 μm,more preferably 75 to 200 μm, in consideration of, among other things,the post-molding rupture strength and shape retainability of thedecorative layer. During the production process of the multilayer filmfor decorative molding, this thickness may be determined by measuringeach layer using a micrometer and performing a calculation uponcompletion of its forming in accordance with JIS C 2151:2006 If themolding film is already laminated with a decorative layer, its thicknesscan be measured by observing the cross section using a differentialinterference microscope, laser microscope, electron microscope, or thelike.

Protective Layer

When applied to a decorative molded body, the protective layer of amultilayer film for decorative molding constitutes the outermost layer.It is therefore preferable that, in addition to being a resin thatleaves intact the mold-conformability during decorative molding of themultilayer film for decorative molding, it be provided withtransparency, glossiness and other esthetic design characteristics, aswell as abrasion resistance, impact resistance, water resistance,chemical resistance, weather resistance and other coat characteristics.With layers located on the nearer side to the decorable object than theprotective layer when a multilayer film for decorative molding becomespart of a decorative molded body, i.e. the color layer, adhesive layerand molding film (only when configuration (ii) or (iii) is used for themultilayer film for decorative molding), mold-conformability duringdecorative molding is generally given priority, with scratch resistancepaid no attention. If, therefore, the protective layer has inferiorscratch resistance, the entire decorative layer becomes eroded, thusexposing the decorable object, and this makes it important that theprotective layer have scratch resistance. As a protective layer withsuch characteristics, a protective layer that contains a polyurethaneresin (U) formed at least from an active hydrogen component (A) and anorganic isocyanate component (B) and having a polycarbonate skeletonwith an alicyclic hydrocarbon group may be used. A polyurethane resinhaving a polycarbonate skeleton with an alicyclic hydrocarbon groupprovides high crystallinity and helps obtain scratch resistance andesthetic design characteristics, as well as making it possible to securemold-conformability during decorative molding.

It is preferable that such a polyurethane resin (U) be a polyurethaneresin formed from an active hydrogen component (A) that contains apolycarbonate polyol (a1) having an alicyclic hydrocarbon group withpreferably a 4 to 10-membered ring (particularly a 6-membered ring) andan organic isocyanate component (B).

Examples of a polycarbonate polyol (a1) having an alicyclic hydrocarbongroup include a polycarbonate polyol produced by having alicyclicmultivalent (di- to trivalent or above) alcohols with a carbon number of6 to 20 or a mixture of these and one or more acyclic multivalent (di-to trivalent or above) alcohols with a carbon number of 2 to 20(preferably alkylene diols having an alkylene group with a carbon numberof 6 to 10, more preferably 6 to 9) undergo a dealcoholizationcondensation reaction with a low molecule carbonate compound (e.g. adialkyl carbonate having an alkyl group with a carbon number of 1 to 6,an alkylene carbonate having an alkylene group with a carbon number of 2to 6, or a diaryl carbonate having an aryl group with a carbon number of6 to 9). Hereinafter, a compound name accompanied by an alphanumericalsymbol, such as “a polycarbonate polyol (a1) having an alicyclichydrocarbon group”, may just be denoted by alphanumerical symbol, suchas “(a1)”.

Examples of an alicyclic multivalent (di- to trivalent or above) alcoholwith a carbon number of 6 to 20 include 1,2-cyclobutanediol,2,2,4,4,-tetramethyl-1,3-cyclobutanediol, 1,2- or 1,3-cyclopentanediol,3-methyl-1,2-cyclopentanediol, 1,2-, 1,3- or 1,4-cyclohexanediol,4-methyl-1,2-cyclohexanediol, 1,2-, 1,3- or 1,4-cyclohexanedimethanol,1,1′-bicyclohexane-1,1′-diol, 1,1′-bicyclohexane-2,2′-diol,1,1′-bicyclohexane-4,4′-diol, a hydrogenated bisphenol A, hydrogenatedbisphenol F, 1,2- or 1,3-cycloheptanediol, 1,2-, 1,4- or1,5-cyclooctanediol and the like. Of these, 1,4-cyclohexanediol andcyclohexanedimethanol, more preferably 1,4-cyclohexanedimethanol, arepreferred from the viewpoint of the scratch resistance andmold-conformability of the protective layer obtained.

Examples of an acyclic multivalent (di- to trivalent or above) alcoholwith a carbon number of 2 to 20 include ethylene glycol, 1,2- or1,3-propylene glycol, diethylene glycol, triethylene glycol, dipropyleneglycol, 1,2-, 1,3-, 2,3- or 1,4-butanediol, 3-methyl-1,2-butanediol,1,2-, 1,4-, 1,5- or 2,4-pentanediol, 2- or 3-methyl-1,5-pentanediol, 2-or 3-methyl-4,5-pentanediol, 2,3-dimethyl trimethylene glycol,2,2,4-trimethyl-1,3-pentanediol, 1,4-, 1,5-, 1,6- or 2,5-hexanediol,1,7-heptanediol, 2- or 3-methyl-1,6-hexanediol, 2-, 3- or4-methyl-1,7-heptanediol, 1,8-octanediol, 2-, 3- or4-methyl-1,8-octanediol, 1,9-nonanediol, 1,12-dodecanediol,neopenthylene glycol, glycerin, trimethylol ethane, trimethylolpropane,a trialkanol amine with a carbon number of 6 to 12, 1,2,6-hexanetriol,pentaerythritol, diglycerin, triglycerin, dipenta erythritol, sorbitol,mannitol and the like. Of these, a linear diol with a carbon number of 3to 6 (1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, and1,6-hexanediol) is preferred from the viewpoint of the scratchresistance and mold-conformability of the protective layer obtained.

Of all polycarbonate polyols (a1) having an alicyclic hydrocarbon group,a polycarbonate diol using alicyclic multivalent (di- to trivalent orabove) alcohols with a carbon number of 6 to 20 and divalent alcohols asacyclic multivalent (di- to trivalent or above) alcohols with a carbonnumber of 2 to 20 to be used as needed, as specified above, arepreferred from the viewpoint of mold-conformability.

The range of the number average molecular weight (hereinafterabbreviated as “Mn”) of a polycarbonate polyol (a1) having an alicyclichydrocarbon group is preferably 500 to 5,000, more preferably 600 to3,000, particularly 750 to 2,000, from the viewpoint of themold-conformability of the protective layer obtained.

Mn may be measured using gel permeation chromatography, for instance,under the following conditions.

Equipment: “HLC-8120GPC” [manufactured by Tosoh Corporation]

Column: “Guard column H_(XL)-H” (one piece) and “TSK gel GMH_(XL)” (twopieces) [both manufactured by Tosoh Corporation]

Sample solution: 0.25 wt % of tetrahydrofuran solution

Solution injection rate: 100 μl

Flow rate: 1 ml/min

Temperature during measurement: 40° C.

Detection device: Refractive index detector

Standard substance: Standard polystyrene

It is preferable that the content of the alicyclic hydrocarbon groupattributed to a polycarbonate polyol (a1) having an alicyclichydrocarbon group in the polyurethane resin (U) be 1 to 30 mass %, morepreferably 5 to 25 mass %, particularly 10 to 20 mass %, relative to thecombined mass of the active hydrogen component (A) and the organicisocyanate component (B) from the viewpoint of the scratch resistanceand esthetic design characteristics of the protective layer.

Apart from a polycarbonate polyol (a1) having an alicyclic hydrocarbongroup, any other polyols used to conventionally produce polyurethane maybe used as part of the active hydrogen component (A). For instance, itis possible to use a polymer polyol (a2) with an Mn of 500 or more otherthan (a1), a polyol containing a carboxyl group and a salt thereof (a3),a chain extender (a4), and a reaction terminator (a5).

Examples of a polymer polyol (a2) with an Mn of 500 or more other than(a1) include a polymer polyol used to conventionally producepolyurethane, e.g. a polyester polyol (a21) and a polyether polyol(a22).

Examples of a polyester polyol (a21) include an aliphatic polycarbonatepolyol not having an alicyclic hydrocarbon group (a211), a dehydrationcondensation-type polyester polyol (a212), a polylactone polyol (a213)and the like.

Examples of an aliphatic polycarbonate polyol not having an alicyclichydrocarbon group (a211) include a polycarbonate polyol produced byhaving one or a mixture of two or more acyclic multivalent (di- totrivalent or above) alcohols with a carbon number of 2 to 20 asspecified above undergo a dealcoholization condensation reaction with alow molecule carbonate compound (e.g. a dialkyl carbonate having analkyl group with a carbon number of 1 to 6, an alkylene carbonate havingan alkylene group with a carbon number of 2 to 6, a diaryl carbonatehaving an aryl group with a carbon number of 6 to 9) and the like.

Specific examples of an aliphatic polycarbonate polyol not having analicyclic hydrocarbon group (a211) include a polyhexamethylene carbonatediol, polypentamethylene carbonate diol, polytetramethylene carbonatediol poly(tetramethylene/hexamethylene) carbonate diol (e.g. a diolobtained by having 1,4-butanediol and 1,6-hexanediol undergo adealcoholization condensation reaction with a dialkyl carbonate) and thelike.

Examples of a dehydration condensation-type polyester polyol (a212)include a polyester polyol formed from alicyclic multivalent (di- totrivalent or above) alcohols with a carbon number of 6 to 20 asspecified above, and/or acyclic multivalent (di- to trivalent or above)alcohols with a carbon number of 2 to 20 as specified above, and amultivalent carboxylic acid with a carbon number of 2 to 10, or anester-forming derivative thereof.

Examples of a multivalent carboxylic acid with a carbon number of 2 to10, or an ester-forming derivative thereof, suitable for use forming adehydration condensation-type polyester polyol (a212) include analiphatic dicarboxylic acid (e.g. succinic acid, adipic acid, azelaicacid, sebacic acid, fumaric acid and maleic acid), an alicyclicdicarboxylic acid (e.g. dimer acid), an aromatic dicarboxylic acid (e.g.terephthalic acid, isophthalic acid and phthalic acid), a trivalent orhigher polycarboxylic acid (e.g. trimellitic acid and pyromelliticacid), an anhydride thereof (e.g. succinic anhydride, maleic anhydride,phthalic anhydride and trimellitic anhydride), an acid halide thereof(e.g. adipic acid dichloride), a low molecular weight alkyl esterthereof (e.g. dimethyl succinate and phthalic acid dimethyl), and amixture thereof.

Specific examples of a dehydration condensation-type polyester polyol(a212) include polyethylene adipate diol, polybutylene adipate diol,polyhexamethylene adipate diol, polyhexamethylene isophthalate diol,polyneopenthylene adipate diol, polyethylene propylene adipate diol,polyethylene butylene adipate diol, polybutylene hexamethylene adipatediol, polydiethylene adipate diol, poly(polytetramethylene ether)adipate diol, poly(3-methyl-pentylene adipate) diol, polyethyleneazelate diol, polyethylene sebacate diol, polybutylene azelate diol,polybutylene sebacate diol, polyneopenthylene terephthalate diol and thelike.

Examples of a polylactone polyol (a213) include a lactonic polyadduct ofan alicyclic multivalent (di- to trivalent or above) alcohol with acarbon number of 6 to 20 as specified above and/or an acyclicmultivalent (di- to trivalent or above) alcohol with a carbon number of2 to 20 as specified above and the like, with lactones with a carbonnumber of 4 to 12 (for instance γ-butrolactone, γ-valerolactone andε-caprolactone) and the like among those suited to this purpose.

Specific examples of a polylactone polyol (a213) includepolycaprolactone diol, polyvalerolactone diol, polycaprolactone trioland the like.

Examples of a polyether polyol (a22) include an aliphatic polyetherpolyol (a221) and an aromatic polyether polyol (a222).

Examples of an aliphatic polyether polyol (a221) include a polyoxyethylene polyol [for instance, polyethylene glycol], polyoxy propylenepolyol (for instance, polypropylene glycol), polyoxy ethylene/propylenepolyol, polyoxy tetramethylene glycol and the like.

Examples of an aromatic polyether polyol (a222) include an ethyleneoxide (hereinafter abbreviated as “EO”) adduct of bisphenol A (forinstance, a 2-mole EO adduct of bisphenol A, a 4-mole EO adduct ofbisphenol A, a 6-mole EO adduct of bisphenol A, an 8-mole EO adduct ofbisphenol A, a 10-mole EO adduct of bisphenol A, or a 20-mole EO adductof bisphenol A), and an propylene oxide (hereinafter abbreviated as“PO”) adduct of bisphenol A (for instance, a 2-mole PO adduct ofbisphenol A, a 3-mole PO adduct of bisphenol A, or a 5-mole PO adduct ofbisphenol A), and other bisphenol-skeletoned polyols, as well as an EOor PO adduct of resorcin.

The Mn of (a2) is preferably 500 to 5,000, more preferably 600 to4,000-particularly 700 to 3,000, from the viewpoint of the scratchresistance and mold-conformability of the protective layer.

Of all (a2) compounds, an aliphatic polycarbonate polyol (a211) nothaving an alicyclic hydrocarbon group is preferred from the viewpoint ofthe weather resistance, water resistance, chemical resistance, scratchresistance and mold-conformability of the protective layer, with apolycarbonate polyol produced by having one or a mixture of two or morelinear diols with a carbon number of 3 to 6 (1,3-propylene glycol,1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol) undergo adealcoholization condensation reaction with a low molecule carbonatecompound as specified above more preferred.

Examples of a polyol containing a carboxyl group and a salt thereof (a3)include a dialkylol alkane acid with a carbon number of 6 to 24 (forinstance, 2,2-dimethylol propionic acid (hereinafter abbreviated as“DMPA”), 2,2-dimethylol butane acid, 2,2-dimethylol heptane acid, or2,2-dimethylol octanoic acid) and the like and a salt thereof. Possibletypes of such a salt include an ammonium salt and an amine salt (forinstance, a salt of a primary amine with a carbon number of 1 to 12(primary monoamine, e.g. methyl amine, ethyl amine, propyl amine andoctyl amine), a salt of secondary monoamine (e.g. dimethyl amine,diethyl amine and dibutylamine) or a salt of tertiary monoamine (e.g.trimethyl amine, triethyl amine, triethanol amine, N-methyl diethanolamine, N,N-dimethyl ethanol amine and some other aliphatic tertiarymonoamine)), and two or more of them may also be used in combination.

Such salts are particular advantageously used when producing apolyurethane resin (U) as a water dispersion as described later, and, ofthem, those whose constituent basic compound has a boiling point of −40°C. to 150° C. at atmospheric pressure are preferable from the viewpointof the water resistance and chemical resistance of the protective layerobtained and the stability of the water dispersion of the urethaneresin. Specific examples include an ammonium salt, triethyl amine salt,N,N-dimethyl ethanol amine salt and the like.

Examples of a chain extender (a4) include water, an acyclic multivalent(di- to trivalent or above) alcohol with a carbon number of 2 to 20 asspecified above, a low-molecular-weight EO and/or PO adducts of such anacyclic polyhydric alcohol (chemical formula weight or Mn being lessthan 500), a diamine with a carbon number of 2 to 10 (e.g. ethylenediamine, propylene diamine, 1,2-propane diamine, butylene diamine,hexamethylene diamine, 2,2,4- or 2,4,4-trimethyl hexamethylene diamine,isophorone diamine and some other aliphatic or alicyclic diamine; o-, m-or p-phenylene diamine, toluene diamine, m-xylylene diamine,4,4′-diaminodiphenyl methane and 4,4′-diamino-3,3′-diethyl diphenylmethane and some other aromatic polyamine), a poly (n=2 to 6) alkylene(with a carbon number of 2 to 6) poly (n=3 to 7) amine (e.g. diethylenetriamine, triethylene tetramine, tetraethylene pentamine andpentaethylene hexamine), hydrazine, a derivative thereof (e.g. a dibasicacid dihydrazide, such as adipic acid dihydrazide) and the like.

Examples of a reaction terminator (a5) include a monoalcohol with acarbon number of 1 to 8 (e.g. methanol, ethanol, isopropanol, butanol,cellosolve or “Carbitol”) and a monoamine with a carbon number of 1 to10 (e.g. monomethyl amine, monoethyl amine, monobutyl amine, dibutylamine, monooctyl amine, monoethanol amine and diethanol amine). Theactive hydrogen component (A) may comprise any one or a combination oftwo or more of (a1) to (a5) and the like.

As part of the organic isocyanate component (B), any isocyanatecompounds used to conventionally produce polyurethane may be used, andthese include, among other things, an alicyclic polyisocyanate (b1) witha carbon number of 6 to 18, an aliphatic polyisocyanate (b2) with acarbon number of 4 to 22, an aromatic polyisocyanate with a carbonnumber of 8 to 26 (b3), an araliphatic polyisocyanate with a carbonnumber of 10 to 18 (b4), and a modified product of such a polyisocyanate(b5). The organic isocyanate component (B) may comprise any one or acombination of two or more of the above.

Examples of an alicyclic polyisocyanate (b1) with a carbon number of 6to 18 include isophorone diisocyanate (hereinafter abbreviated as“IPDI”), 4,4-dicyclohexyl methane diisocyanate (hereinafter abbreviatedas hydrogenerated “MDI”), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate,bis(2-isocyanato-ethyl)-4-cyclohexene-1,2-dicarboxylate, 2,5- or2,6-norbornane diisocyanate and the like.

Examples of an aliphatic polyisocyanate (b2) with a carbon number of 4to 22 include ethylene diisocyanate, tetramethylene diisocyanate,hexamethylene diisocyanate (hereinafter abbreviated as “HDI”), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanato-methylcaproate, bis(2-isocyanato-ethyl) fumarate, bis(2-isocyanato-ethyl)carbonate, 2-isocyanato-ethyl-2,6-diisocyanato-hexanoate and the like.

Examples of an aromatic polyisocyanate with a carbon number of 8 to 26(b3) include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylenediisocyanate (hereinafter abbreviated as “TDI”), crude TDI, 4,4′- or2,4′-diphenyl methane diisocyanate (hereinafter abbreviated as “MDI”),crude MDI, polyaryl polyisocyanate, 4,4′-diisocyanato-biphenyl,3,3′-dimethyl-4,4′-diisocyanato-biphenyl,3,3′-dimethyl-4,4′-diisocyanato-diphenyl methane, 1,5-naphthylenediisocyanate, 4,4′,4″-triphenyl methane triisocyanate, m- orp-isocyanato-phenylsulfonyl isocyanate and the like.

Examples of an araliphatic polyisocyanate (b4) with a carbon number of10 to 18 include m- or p-xylylene diisocyanate α,α,α′,α′-tetramethylxylylene diisocyanate and the like.

Examples of a modified product (b5) of polyisocyanate (b1) to (b4)include a modified product of polyisocyanate containing a urethanegroup, carbodiimide group, allophanate group, urea group, biuret group,urethodione group, urethoimine group, isocyanurate group, or oxazolidonegroup (with a normal free isocyanate group content of 8 to 33 mass %,preferably 10 to 30 mass %, particularly 12 to 29 mass %). Specificexamples include a modified MDI (e.g. a urethane-modified MDI,carbodiimide-modified MDI, and trihydrocarbyl phosphate-modified MDI),urethane-modified TDI, biuret-modified HDI, isocyanurate-modified HDI,and isocyanurate modified IPDI.

Of all constituent components of the organic isocyanate component (B),an alicyclic polyisocyanate (b1) with a carbon number of 6 to 18 and analiphatic polyisocyanate (b2) with a carbon number of 4 to 22 arepreferred from the viewpoint of the weather resistance of the protectivelayer obtained, with an alicyclic diisocyanate with a carbon number of 6to 18 and an aliphatic diisocyanate with a carbon number of 4 to 22further preferred, particularly IPDI, hydrogenated MDI, HDI and amixture thereof and more particularly IPDI, a hydrogenated MDI and amixture thereof. Of these, a hydrogenated MDI is most preferred.

It is preferable that, from the viewpoint of the scratch resistance andmold-conformability of the protective layer obtained, the combinedconcentration of the urethane groups and urea groups present in thepolyurethane resin (U) be 1.0 to 6.0 m mol/g, more preferably 1.5 to 5.0m mol/g, particularly 2.0 to 4.0 m mol/g, according to the weight of(U).

Suitably adjusting the types and molecular weights of the activehydrogen component (A) and organic polyisocyanate component (B), as wellas the moisture content of the reaction system and the like, makes itpossible to bring the combined concentration of the urethane groups andurea groups present in the polyurethane resin (U) to the desired range.

It is preferable that, from the viewpoint of the water resistance,chemical resistance and mold-conformability of the protective layerobtained, the Mn of the polyurethane resin (U) be 10,000 to 1,000,000,more preferably 10,000 to 500,000, particularly 10,000 to 200,000, andmost preferably 10,000 to 100,000.

It is preferable that, from the viewpoint of the mold-conformability ofthe protective layer obtained, the melting temperature of thepolyurethane resin (U) be 50 to 280° C., more preferably 60 to 200° C.,particularly 80 to 160° C.

The melting temperature of the polyurethane resin (U) is the temperatureat which the melt mass flow rate becomes 10 g/10 minutes as measured ata load of 2.16 kg under JIS K 7210: 1999 (a test method for melt massflow rates of plastics—thermoplastic plastics) using a “Melt IndexerModel I” manufactured by Tester Sangyo Co. Ltd. as melt mass flow ratemeasurement equipment.

It is further necessary that, to improve the water resistance, chemicalresistance and scratch resistance of the protective layer obtainedwithout harming mold-conformability during decorative molding, condition(1) and/or condition (2) below be satisfied.

Condition (1): The polyurethane resin (U) is a polyurethane resin (U1)that has an alkoxysilyl group and/or a silanol group in each molecule.

Condition (2): The protective layer contains a compound (X) that has aglycidyl ether group, and an alkoxysilyl group and/or a silanol group,and the polyurethane resin (U) is a polyurethane resin (U2) that has anamino group, or a carboxyl group and/or a salt thereof.

Examples of a method to produce a polyurethane resin (U) having analkoxysilyl group and/or a silanol group in each molecule as specifiedin condition (1) include a method that lets a polyurethane resin (U2)having an amino group, or a carboxyl group and/or a salt thereof, and acompound (X) having a glycidyl ether group, and an alkoxysilyl groupand/or a silanol group in the molecule react with each other (1-1) and amethod that lets a polyurethane resin having an isocyanate group and acompound (Y) having an amino group, and alkoxysilyl group and/or asilanol group in the molecule react with each other (1-2).

Examples of a compound (X) used in method (1-1) include a glycidoxyalkyltrialkoxysilane with a carbon number of 7 to 20, a glycidoxyalkyl(alkyl) dialkoxysilane with a carbon number of 7 to 20, a glycidoxyalkyl(dialkyl) alkoxysilane with a carbon number of 7 to 20, and ahydrolysate thereof (a compound having a silanol group derived from anyof the aforementioned compounds by converting an alkoxy group containedtherein to a hydroxyl group). Specific examples include 3-glycidoxypropyl trimethoxysilane, 3-glycidoxy propyl triethoxysilane, 3-glycidoxypropyl methyl dimethoxy silane and 3-glycidoxy propyl methyl diethoxysilane and the like, and a hydrolysate thereof (a compound having asilanol group derived from any of the aforementioned compounds byconverting an alkoxy group contained therein to a hydroxyl group). Alltypes of compound (X) may be used singly or in combination of two ormore.

Examples of a method to produce an amino group-variety of thepolyurethane resin (U2) having an amino group, or a carboxyl groupand/or a salt thereof, used in method (1-1) include a method based onthe introduction of terminal amine groups using a polyfunctional amine,such as a diamine with a carbon number of 2 to 10 or a poly (n=2 to 6)alkylene (with a carbon number of 2 to 6) poly (n=3 to 7) amine and thelike, as exemplified as a chain extender (a4) in the description of theproduction of a polyurethane resin, a method based on the introductionof terminal isocyanate groups by making the molar quantity of isocyanategroups excessive with respect to active hydrogens that react withisocyanate groups (e.g. hydroxyl groups and amino groups) during thereaction between the active hydrogen component (A) and the organicisocyanate component (B), followed by the conversion thereof intoterminal amino groups through a reaction with water, and a method basedon the introduction of ketimine bonds to resin terminals using amonoamine having ketimine bonds (—C═N—), followed by the conversion ofketimine bonds to terminal amino groups via hydrolysis and the like.

There are no specific limitations on the monoamine having a ketiminebond described above as long as it contains at least one amino group andat least one ketimine bond in a molecule. Examples include a ketiminecompound obtained by letting a diamine with a carbon number of 2 to 10or a poly (n=2 to 6) alkylene (with a carbon number of 2 to 6) poly (n=3to 7) amine, as exemplified as a chain extender (a4), and a ketone reactwith each other. It is preferable that from the viewpoint of the easyevaporability of a ketone during the production of amino groups throughthe hydrolysis of ketimine bonds, the ketone is a ketone having aboiling point of 120° C. or less, such as acetone, diethyl ketone,methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketonemethyl isobutyl ketone and the like.

Examples of a method to obtain a carboxyl group and/or a salt thereof ofa polyurethane resin (U2) having an amino group, or a carboxyl groupand/or a salt thereof, used in method (1-1) include a method based onthe use of a polyol containing a carboxyl group and a salt thereof (a3)as part of the active hydrogen component (A) during the production of aurethane resin.

The temperature, duration and other conditions for the reaction betweena glycidyl ether group and an amino group, or a carboxyl group and/or asalt thereof, may be on par with those usually applied to these groups.

Examples of a compound (Y) used in method (1-2) include an aminoalkyltrialkoxysilane with a carbon number of 4 to 20, aminoalkyl (alkyl)dialkoxysilane with a carbon number of 4 to 20, aminoalkyl (dialkyl)alkoxysilane with a carbon number of 4 to 20 and a hydrolysate thereof(a compound having a silanol group derived from any of theaforementioned compounds by converting an alkoxy group contained thereinto a hydroxyl group). Specific examples include 3-aminopropyltriethoxysilane, 3-aminopropyl trimethoxysilane,N-2-(aminoethyl)-3-aminopropyl triethoxysilane,N-2-(aminoethyl)-3-aminopropyl trimethoxysilane,N-2-(aminoethyl)-3-aminopropyl methyl dimethoxy silane, and ahydrolysate thereof (a compound having a silanol group derived from anyof the aforementioned compounds by converting an alkoxy group containedtherein to a hydroxyl group). All types of compound (Y) may be usedsingly or in combination of two or more.

Examples of a method to produce a polyurethane resin having anisocyanate group used in method (1-2) include a method based on theintroduction of terminal isocyanate groups by making the molar quantityof isocyanate groups excessive with respect to active hydrogens (e.g.hydroxyl groups and amino groups) that react with isocyanate groupsduring the reaction between the active hydrogen component (A) and theorganic isocyanate component (B).

When the polyurethane resin (U) is a polyurethane resin (U1) having analkoxysilyl group and/or a silanol group in each molecule, a protectivelayer excellent in water resistance, chemical resistance and scratchresistance can be obtained as a result of excellent mold-conformabilityprior to heating or the like as part of decorative molding and thecrosslinking of alkoxysilyl groups and/or silanol groups and theresulting formation of a crosslinked structure during heating or thelike as part of decorative molding.

A compound (X) used in method (1-1) may be used as a compound (X) havinga glycidyl ether group, and an alkoxysilyl group and/or a silanol group,as specified under condition (2). Similarly, a polyurethane resin (U2)having an amino group, or a carboxyl group and/or a salt thereof, usedin method (1-1) may be used as a polyurethane resin (U2) having an aminogroup, or a carboxyl group and/or a salt thereof, as specified undercondition (2).

When the polyurethane resin (U2) as specified under condition (2) is thekind that has a carboxyl group and/or a salt thereof it is preferablethat the amount of the carboxyl group and a salt thereof in thepolyurethane resin is equal to or greater than the number of moles ofthe glycidyl ether group contained in the compound (X) from theviewpoint of reactivity with the compound (X), while it is alsopreferable that the amount of the carboxyl group and a salt thereof inthe polyurethane resin is suited to make their content in thepolyurethane resin 1.3 m mol/g or less after the reaction with thecompound (X) from the viewpoint of water resistance and chemicalresistance.

The content of the carboxyl group in the polyurethane resin may becalculated from the acid value as measured using the method described inJIS K 0070: 1992 (potentiometric titration method) when the residueobtained by heat-drying 3 to 10 g of the polyurethane resin (U) at 130°C. for 45 minutes is, after rinsing, heat-dried at 130° C. for 45minutes again and dissolved in dimethyl formamide.

When the apolyurethane resin (U2) as specified under condition (2) isthe kind that has an amino group, it is preferable that the amount ofthe amino group in the polyurethane resin is equal to or greater thanthe number of moles of the glycidyl ether group contained in thecompound (X) from the viewpoint of reactivity with the compound (X),while it is also preferable that the amount of the amino group in thepolyurethane resin is suited to make its content in the polyurethaneresin (U) 0.35 m mol/g or less after the reaction with the compound (X)from the viewpoint of water resistance and chemical resistance.

Examples of a method to let the protective layer contain a compound (X)to satisfy condition (2) include a method based on the use of apolyurethane resin composition produced by mixing a polyurethane resin(U2) having an amino group, or a carboxyl group and/or a salt thereof,and a compound (X) in advance and a method based on the mixing of apolyurethane resin (U2) and a compound (X) during the production of themultilayer film for decorative molding.

The temperature, duration and other conditions for the reaction betweena glycidyl ether group and an amino group, or a carboxyl group and/or asalt thereof, may be on par with those usually applied to these groups.

If the protective layer is made to contain a compound (X), a protectivelayer excellent in water resistance, chemical resistance and scratchresistance can be obtained as a result of excellent mold-conformabilityprior to heating or the like as part of decorative molding and areaction between the glycidyl ether group contained in the compound (X)and the amino group, or a carboxyl group and/or a salt thereof,contained in the polyurethane resin (U2), as well as the crosslinking ofalkoxysilyl groups and/or silanol groups introduced into thepolyurethane resin by the compound (X) and the resulting formation of acrosslinked structure in the process of the above reaction duringheating of the like as part of decorative molding.

It is preferable that, from the viewpoint of the water resistance,chemical resistance and scratch resistance, as well asmold-conformability, of the protective layer obtained, the amount of (X)and/or (Y) used is an amount that makes the combined mass fraction of Siatoms attributed to the alkoxysilyl group and/or the silanol groupcontained in (X) and/or (Y) 0.05 to 2.0 mass %, more preferably 0.1 to1.5 mass %, particularly 0.2 to 1.0 mass %, relative to the combinedmass of (A) and (B).

It is preferable that polyurethane resin (U) is amenable to use as asolvent solution or water dispersion from the viewpoint of coatabilityduring the formation of the multilayer film for decorative molding. Asthe method to prepare a solvent solution or water dispersion of thepolyurethane resin (U), any known technique may be used.

Examples of a solvent solution preparation method include a techniquedesigned to let the ingredients react in a solvent and a techniquedesigned to dissolve a polyurethane resin (U) in a solvent after havingit undergo a reaction under solventless conditions.

Examples of a solvent include a generally known organic solvent, such asa solvent based on a ketone with a carbon number of 3 to 10 (e.g.acetone, methyl ethyl ketone, and methyl isobutyl ketone), a solventbased on an ester with a carbon number of 2 to 10 (e.g. ethyl acetate,butyl acetate or γ-butyrolactone), a solvent based on an ether with acarbon number of 4 to 10 (e.g. tetrahydrofuran and diethylene glycoldimethyl ether), a solvent based on an amide with a carbon number of 3to 10 (e.g. N,N-dimethyl formamide, N,N-dimethyl acetamide,N-methyl-2-pyrolidone, and N-methyl caprolactam), a solvent based on analcohol with a carbon number of 1 to 8 (e.g. methanol, ethanol,isopropyl alcohol and octanol), and a solvent based on a hydrocarbonwith a carbon number of 4 to 10 (e.g. n-butane, cyclohexane, toluene,and xylene).

Of these, it is preferable to use a polar solvent with a boiling pointof 100° C. or less such as acetone, methyl ethyl ketone, ethyl acetate,tetrahydrofuran and isopropyl alcohol, from the viewpoint of thesolubility of the polyurethane resin (U) and its dryability during theproduction of a protective layer.

Examples of a preparation method for a water dispersion include aprepolymer mixing method as described in Japanese Unexamined PatentPublication (Kokai) No. 2004-2732, Official Gazette, and a methoddesigned to form a dead polymer of a urethane resin and disperse it inwater as described in International Publication WO 2010/122599.

It is preferable that, when obtaining an aqueous dispersion of apolyurethane resin (U), a polyolcontaining a carboxyl group and a saltthereof (a3) is used as part of the active hydrogen component (A) fromthe viewpoint of dispersion stability, as well as the water resistanceand chemical resistance of the resin.

The content of the carboxyl group and a salt thereof attributed to apolyolcontaining a carboxyl group and a salt thereof (a3) present in thepolyurethane resin (U), in the case of obtaining an aqueous dispersion,is preferably 0.05 to 1.3 m mol/g, more preferably 0.1 to 1.1 m mol/g,particularly 0.15 to 0.90 m mol/g-relative to the combined mass of theactive hydrogen component (A) and the organic isocyanate component (B)from the viewpoint of dispersion stability, as well as the waterresistance and chemical resistance of the protective layer obtained.

When the polyurethane resin (U), in the case of obtaining an aqueousdispersion, is a polyurethane resin (U1) having an alkoxysilyl groupand/or a silanol group in each molecule as described above, the use of apolyolcontaining a carboxyl group and a salt thereof (a3) as part of theactive hydrogen component (A) for preparing (U1) makes it possible tointroduce a carboxyl group and a salt thereof into (U1).

When the polyurethane resin (U), in the case of obtaining an aqueousdispersion, is a carboxyl group and a salt thereof-variety of apolyurethane resin (U2) having an amino group, or a carboxyl groupand/or a salt thereof, the carboxyl group and a salt thereof introducedto confer dispersion stability on this polyurethane resin alsocontributes to the reaction with a compound (X) having a glycidyl ethergroup, and an alkoxysilyl group and/or a silanol group, as describedabove.

Examples of a method forming a protective layer using a polyurethaneresin (U) include the following:

A solvent solution of a polyurethane resin (U) or a water dispersion ofa polyurethane resin (U) can be used to form a polycarbonate-basedpolyurethane layer by thinly and uniformly coating a molding film withit using a generally known coating method (e.g. bar coating, rollcoating, gravure coating, curtain coating, spray coating and silk screenprinting) and having it undergo a reaction inside a hot air oven.

A protective layer formed from a polyurethane resin (U) in this mannermay contain resins other than a polyurethane resin (U), including, forinstance, an acrylic-based polyurethane, polyether-based polyurethane,and polyester-based polyurethane.

A protective layer may also contain a curing accelerator, binding agent,surface adjustor, pigment, dye, plasticizer, ultraviolet absorber,photostabilizer, and the like, as needed. It is preferable that thetotal content of resins other than a polycarbonate-based polyurethaneresin and additives in the protective layer is 15 mass % or less, morepreferably 10 mass % or less, relative to the total mass of thepolyurethane resin (U) as reference. If resins other than apolycarbonate-based polyurethane resin are contained by a greater amountthan the above range, there is a risk that the requisite performance ofa protective layer may not be obtained.

The thickness of the protective layer is preferably 10 to 70 μm, morepreferably, 20 to 50 μm. If the thickness is 10 μm or more as preferred,it is easier to confer coat characteristics. If the thickness is 70 μmor less as preferred, it is easier to form a color layer over it as thisis a moderate thickness consistent with a flat surface. During theproduction process of the multilayer film for decorative molding, thisthickness may be determined by measuring each layer using a micrometerand performing a calculation upon completion of its forming inaccordance with JIS C 2151:2006. If the molding film is alreadylaminated with a decorative layer, its thickness can be measured byobserving the cross section using a differential interferencemicroscope, laser microscope, electron microscope, or the like.

Color Layer

There are no specific limitations on the color layer used for amultilayer film for decorative molding as long as it is capable ofconferring an intended color, texture and the like on the decorableobject to be decorated and having concealability upon being molded aspart of the decorative molded body. It may, for instance, be a coloredresin layer, prepared by mixing a binder resin with a pigment and dye,or a thin metal film layer. A colored resin layer prepared by mixing abinder resin and pigment is more preferable from the viewpoint of easeof color adjustment and good mold-conformability during decorativemolding.

The binder resin to be used for a colored resin layer may be athermosetting resin, thermoplastic resin or light curing resin. Examplesof a thermosetting resin include an unsaturated polyester resin, phenolresin, epoxy resin, acrylic resin, urethane resin, melamine resin, urearesin and polycarbonate resin. Examples of a thermoplastic resin includea polyethylene resin, polypropylene resin, polycarbonate resin, acrylicresin and polystyrol resin. Examples of a light curing resin include aurethane acrylate resin, polyester acrylate resin, unsaturated polyesterresin, silicone acrylate resin and epoxy acrylate resin. It is possibleto use one or more of the above blended with a photopolymerizationinitiator and the like as needed. Needless to say, these resins may alsobe blended with a curing agent, curing accelerator, binding agent,surface adjustor, plasticizer, ultraviolet absorber, photostabilizer andother additives, as needed. Though such a resin may be a copolymer or amixture of different kinds of resins, a thermosetting resin may beadvantageously used as it is easy to handle and cheap with good heatresistance. From the viewpoint of mold-conformability during decorativemolding, it is particularly desirable to use a resin mixture containinga urethane resin and acrylic resin as a binder resin.

Both inorganic and organic pigments can be used. Examples includealuminum powder, carbon black, titanium dioxide, mica, phthalocyaninegreen and dioxazine violet. Such pigments may be used singly or as amixture of two or more. The concentration of a pigment may be adjustedwithin a range that does not impair the effect of the present invention.

The thickness of the color layer is preferably 15 to 50 μm and morepreferably 20 to 40 μm. If the thickness is 15 μm or more as preferred,it is easier to obtain a color layer with an intended color tone. If thethickness is 50 μm or less as preferred, it is easier to form anadhesive layer over it as this is a moderate thickness consistent with aflat surface. During the production process of the multilayer film fordecorative molding, this thickness may be determined by measuring eachlayer using a micrometer and performing a calculation upon completion ofits forming in accordance with JIS C 2151:2006. If the molding film isalready laminated with a decorative layer, its thickness can be measuredby observing the cross section using a differential interferencemicroscope, laser microscope, electron microscope, or the like.

Adhesive Layer

On top of a molding film and a color layer, a multilayer film fordecorative molding also features an adhesive layer. The presence of anadhesive layer makes it possible to stretch the multilayer film fordecorative molding during the molding process, while, at the same time,providing bonding to the decorable object. There are no specificlimitations on the adhesive layer as long as it is adhesive to thedecorable object. Examples of an adhesive include an acrylic adhesive,urethane-based adhesive, polyester-based adhesive and olefin-basedadhesive. The thickness of the adhesive layer is preferably 5 to 50 μmand more preferably 10 to 40 μm. If the thickness is 5 μm or more aspreferred, it is easier to provide bonding to the decorable object. Ifthe thickness is 50 μm or less as preferred, a good appearance can beobtained as this is a moderate thickness consistent with a flat surface.Usually, this thickness can be measured using a micrometer in accordancewith JIS C 2151: 2006. If the decorative layer is already laminated withthe molding film, it is possible to measure the thickness of theadhesive layer by observing the cross section using a differentialinterference microscope, laser microscope, electron microscope, or thelike.

Preparation Method for Decorative Molded Body

There are no specific limitations on the preparation method for adecorative molded body as long as it is a generally known thermoformingmethod capable of decorating a decorable object with a three-dimensionalshape, including, among other things, vacuum molding and air-pressureforming. However, it is preferable that, from the viewpoint ofmold-conformability during decorative molding and adhesiveness to thedecorable object, a thermoforming method designed to bond the multilayerfilm for decorative molding onto the decorable object by heating it to atemperature equal to or greater than the softening point of theconstituent layer of the decorative layer with the highest softeningpoint under reduced pressure conditions and bringing its adhesive layerinto contact with the surface of the decorable object.

EXAMPLES

Our resins, films and methods will now be illustrated in greater detailwith reference to examples below. However, it should be understood thatthis disclosure is not construed as being limited thereto. Hereinafter,the term “parts” refers to parts by mass.

Working Example 1

In a simple pressure reaction apparatus equipped with a stirrer andheater, 165.5 parts of a polycarbonate diol with an Mn of 1,000resulting from a reaction between 1,4-cyclohexanedimethanol and anethylene carbonate as (a1), 66.2 parts of a polycarbonate diol with anMn of 2,000 resulting from a reaction between a mixture of1,4-butanediol and 1,6-hexanediol (molar ratio 70:30) and an ethylenecarbonate as (a2), 21.3 parts of DMPA as (a3), 0.26 parts of ethyleneglycol as (a4), 104.4 parts of IPDI as the organic polyisocyanatecomponent (B) and 153.3 parts of acetone as a reaction solvent wereplaced and stirred at 85° C. for 15 hours, leading to a urethanationreaction, with an acetone solution of a urethane prepolymer havingterminal isocyanate groups obtained as a result. After this, whileproviding stirring at 40° C., 12.9 parts of triethyl amine as aneutralization agent and 623.9 parts of water were added. Afterproviding stirring at 60 rpm for 3 minutes, 1.5 parts of 3-aminopropyltrimethoxysilane as a compound (Y) and 3.6 parts of ethylene diamine as(a4) were added, and acetone was removed by evaporation under reducedpressure conditions at 65° C. over 8 hours, with 1,000 parts of a waterdispersion of a polyurethane resin (U1-1) having a silanol group in eachmolecule obtained as a result.

Next, the preparation method for a multilayer film for decorativemolding is described. As a molding film 1, a dry laminate of a 100μm-thick unstretched polyethylene terephthalate film (manufactured byToray Industries, Inc., FL10), coated with a urethane-based adhesive(TR-7233, manufactured by Shin-Nakamura Chemical Co., Ltd.) to apost-drying thickness of 0.5 μm using a bar coater, and a 40 μm-thickunstretched polypropylene film (manufactured by Mitsui ChemicalsTohcello Inc., SC) was used. The molding film was coated with a waterdispersion of a polyurethane resin (U1-1) as described above to athickness equivalent to a post-drying thickness of 40 μm on theunstretched polypropylene film side using an applicator and then driedat 80° C. for 10 minutes, with a protective layer 2 formed in theprocess. Next, the protective layer 2 formed on the molding film 1 wascoated with a paint (manufactured by Nippon Bee Chemical, R2325) forforming a color layer 3 to a thickness equivalent to a post-dryingthickness of 40 μm using an applicator and then dried at 80° C. for 10minutes, with a color layer 3 formed in the process. After this, thecolor layer 3 formed on the protective layer 2, itself formed on themolding film 1, was coated with a paint (manufactured by Toyobo Co.,Ltd., M-28) for forming an adhesive layer 4 to a thickness equivalent toa post-drying thickness of 20 μm using an applicator and then dried at80° C. for 10 minutes, with an adhesive layer 4 formed in the process.In this manner, a multilayer film for decorative molding as illustratedin FIG. 1 was obtained.

Working Example 2

A protective layer 2 was formed on the molding film 1 using the samemethod as working example 1, except that a 100 μm-thick unstretchedpolyethylene terephthalate film (manufactured by Toray Industries, Inc.,FL10) was just used as the molding film 1. A color layer 3 was thenformed using the same method as working example 1, except that the colorlayer 3 was formed on the side of the molding film 1 opposite to theprotective layer 2. Next, an adhesive layer 4 was formed on the colorlayer 3 using the same method as working example 1. In this manner, amultilayer film for decorative molding as illustrated in FIG. 2 wasobtained.

Working Example 3

First, a color layer 3 was formed on the molding film 1 using the samemolding film 1 as working example 2 and under the same color layercoating conditions as working example 2. A protective layer 2 was thenformed on the color layer 3, itself formed on the molding film 1, underthe same coating conditions as working example 1. Next, an adhesivelayer 4 was formed using the same method as working example 1, exceptthat the adhesive layer 4 was formed on the molding film 1 on the sideopposite to the protective layer 2, which had been formed on the colorlayer 3, itself formed on the molding film 1. In this manner, amultilayer film for decorative molding as illustrated in FIG. 3 wasobtained.

Working Example 4

A water dispersion of a polyurethane resin (U1-2) having a silanol groupin each molecule was obtained in the same manner as working example 1,except that the types and amounts used of the input materials werechanged to those specified in Table 1. A multilayer film for decorativemolding was then obtained using the same method as working example 1,except that the polyurethane resin (U1-2) was used.

Working Example 5

In a simple pressure reaction apparatus equipped with a stirrer andheater, 147.7 parts of a polycarbonate diol with an Mn of 900 resultingfrom a reaction between a mixture of 1,4-cyclohexanedimethanol and1,6-hexanediol (molar ratio 50:50) and ethylene carbonate as (a1), 65.6parts of a polycarbonate diol with an Mn of 2,000 resulting from areaction between a mixture of 1,4-butanediol and 1,6-hexanediol (molarratio 70:30) and ethylene carbonate as (a2), 21.3 parts of DMPA as (a3),0.26 parts of ethylene glycol as (a4), 122.8 parts of hydrogenated MDIas the organic polyisocyanate component (B) and 153.3 parts of acetoneas a reaction solvent were placed and stirred at 85° C. for 15 hours,leading to a urethanation reaction, with an acetone solution of aurethane prepolymer having terminal isocyanate groups obtained as aresult. 511 parts of the acetone solution of the resulting urethaneprepolymer was fed to the simple pressure reaction apparatus, and, whileproviding stirring at 40° C., 12.9 parts of triethyl amine as aneutralization agent and 623.9 parts of water were added. Afterproviding stirring at 60 rpm for 3 minutes, 3.6 parts of ethylenediamine as (a4) was added, and acetone was removed by evaporation underreduced pressure conditions at 65° C. over 8 hours, followed by theaddition at 30° C. of 15.3 parts of 3-glycidoxy propyl trimethoxysilaneas a compound (X) and 10 minutes of stirring, with 1,000 parts of awater dispersion containing a polyurethane resin (U2-1) having acarboxyl group and a salt thereof in each molecule and 3-glycidoxypropyl silane triol obtained as a result. Next, a multilayer film fordecorative molding was obtained using the same method as working example1, except that a water dispersion (U2-1) containing the polyurethaneresin and 3-glycidoxy propyl silane triol was used.

Working Example 6

Under nitrogen atmosphere, 13.1 parts of a polycarbonate diol with an Mnof 900 resulting from a reaction between a mixture of1,4-cyclohexanedimethanol and 1,6-hexanediol (molar ratio 50:50) andethylene carbonate as (a1), 116.8 parts of a polycarbonate diol with anMn of 1,000 resulting from a reaction between a mixture of1,4-butanediol and 1,6-hexanediol (molar ratio 70:30) and ethylenecarbonate as (a2), 34.4 parts of DMPA as (a3), 5.1 parts of ethyleneglycol as (a4) and 119.6 parts of hydrogenated MDI as (B) were placed ina KRC kneader [manufactured by Kurimoto, Ltd.], a biaxial kneadingmachine, and kneaded at 220° C. for 10 minutes, leading to aurethanation reaction. The reaction product was taken out and, afterbeing squeezed flat using a compression press heated to 180° C., cutusing an angular pelletizer [manufactured by Horai Co., Ltd.], with apolyurethane resin obtained as a result. Next, 289 parts of the obtainedpolyurethane resin, 14 parts of 25 mass % aqueous ammonia as aneutralization agent and 660.5 parts of water were placed in atemperature-controllable pressure-resistant vessel and subjected to adispersion treatment at 150° C. and 12,000 rpm for 3 minutes using aClearmix dispersing machine [manufactured by M Techniqute Co. Ltd.],with a water dispersion of a polyurethane resin obtained. With 36.5parts of 3-glycidoxy propyl trimethoxysilane as a compound (X) added,963.5 parts of the obtained water dispersion of a polyurethane resin wasthen stirred at 30° C. for 10 minutes, with 1,000 parts of a waterdispersion containing a polyurethane resin (U2-2) having a carboxylgroup and a salt thereof in each molecule and 3-glycidoxy propyl silanetriol obtained. Next, a multilayer film for decorative molding wasobtained using the same method as working example 1, except that a waterdispersion containing a polyurethane resin (U2-2) having a carboxylgroup and a salt thereof in each molecule and 3-glycidoxy propyl silanetriol was used.

Working Examples 7 to 9

A water dispersion containing one of the polyurethane resins (U2-3) to(U2-5) having a carboxyl group and a salt thereof in each molecule and3-glycidoxy propyl silane triol was obtained in the same manner asworking example 4, except that the types and amounts used of the inputmaterials were changed to those specified in Table 1. A multilayer filmfor decorative molding was then obtained using the same method asworking example 1, except that a water dispersion containing one of thepolyurethane resins (U2-3) to (U2-5) having a carboxyl group and a saltthereof in each molecule and 3-glycidoxy propyl silane triol was used.

Comparative Example 1

A water dispersion containing a polyurethane resin (U2′-1) having acarboxyl group and a salt thereof in each molecule and 3-glycidoxypropyl silane triol was obtained in the same manner as working example6, except that the types and amounts used of the input materials werechanged to those specified in Table 1. A multilayer film for decorativemolding was then obtained using the same method as working example 1,except that a water dispersion containing a polyurethane resin (U2′-1)having a carboxyl group and a salt thereof in each molecule and3-glycidoxy propyl silane triol was used.

Comparative Example 2

A water dispersion of a polyurethane resin (U2′-2) having a carboxylgroup and a salt thereof in each molecule was obtained in the samemanner as working example 6, except that the types and amounts used ofthe input materials were changed to those specified in Table 1 and thata compound (X) was not added. A multilayer film for decorative moldingwas then obtained using the same method as working example 1, exceptthat a water dispersion of the polyurethane resin (U2′-2) was used.

TABLE 1 Working Working Working Working Working Working Working WorkingWorking Comparative Comparative example 1 example 2 example 3 example 4example 5 example 6 example 7 example 8 example 9 example 1 example 2Type of polyurethane resin (U) U1-1 U1-1 U1-1 U1-2 U2-1 U2-2 U2-3 U2-4U2-5 U2′-1 U2′-2 Active (a1) A polycarbonate diol with an Mn of 1,000parts by 165.5 165.5 165.5 — — — — — 122.3 — — hydrogen resulting from areaction between mass component 1,4-cyclohexanedimethanol and an (A)ethylene carbonate A polycarbonate diol with an Mn of 900 parts by — — —152.7 147.7 13.1 79.0 108.9 — — 90.3 resulting from a reaction between amass mixture of 1,4-cyclohexanedimethanol and 1,6-hexanediol (molarratio 50:50) and ethylene carbonate (a2) A polycarbonate diol with an Mnof 2,000 parts by 66.2 66.2 66.2 67.9 65.6 — — — — — 64.5 resulting froma reaction between a mass mixture of 1,4-butanediol and 1,6-hexanediol(molar ratio 70:30) and an ethylene carbonate A polycarbonate diol withan Mn of 2,000 parts by — — — — — — — — — 135.9 — resulting from areaction between a mass mixture of 1,3-propanediol and 1,4-butanediol(molar ratio50:50) and ethylene carbonate A polycarbonate diol with anMn of 1,000 parts by — — — — — 116.8 12.1 38.9 61.2 22.7 — resultingfrom a reaction between a mass mixture of 1,4-butanediol and1,6-hexanediol (molar ratio 70:30) and ethylene carbonate (a3) DMPAparts by 21.3 21.3 21.3 21.3 21.3 34.4 35.3 35.1 34.9 39.7 40.2 mass(a4) Ethylene glycol parts by 0.26 0.26 0.26 0.26 0.26 5.1 18.0 3.0 0.381.60 1.00 mass Ethylene diamine parts by 3.6 3.6 3.6 3.6 3.6 — — — — — —mass Organic IPDI parts by 104.4 104.4 104.4 53.0 — — — — — — —polyisocyanate mass component (B) MDI-H parts by — — — 62.5 122.8 119.6125.3 89.6 — 79.5 85.8 mass HDI parts by — — — — — — 26.8 19.1 74.1 17.018.3 mass Reaction solvent Acetone parts by 153.3 153.3 153.3 153.3153.3 — — — — — — mass Neutralization agent Triethyl amine parts by 12.912.9 12.9 13.0 13.0 — — — — — — mass 25 mass % aqueous ammonia parts by— — — — — 14.0 14.3 14.2 14.2 16.1 16.3 mass Water parts by 623.9 623.9623.9 623.9 623.9 660.5 676.7 672.6 668.3 675.0 683.6 mass Compound (X)3-glycidoxy propyl trimethoxysilane parts by — — — — 15.3 36.5 12.5 18.624.6 12.5 0 mass 3-glycidoxy propyl methyl dimethoxy silane parts by — —— — — — — — — — — mass Compound (Y) 3-aminopropyl trimethoxysilane partsby 1.5 1.5 1.5 5.8 — — — — — — — mass Properties Mass fraction of thealicyclic hydrocarbon mass % 27.4 27.4 27.4 11.0 11.0 1.3 7.6 10.0 25.00.0 8.1 group contained in (a1) relative to combined mass of (A) and (B)Total content of the carboxyl group and mmol/g 0.45 0.45 0.45 0.45 0.450.89 0.89 0.89 0.89 1.00 1.00 a salt thereof attributed to (a3) presentin (U) Combined concentration of the urethane mmol/g 2.5 2.5 2.5 2.5 2.53.2 4.5 3.1 3.0 2.7 2.9 groups and urea groups present in (U) Massfraction of Si atoms attributed to the mass % 0.07 0.07 0.07 0.25 0.51.5 0.5 0.74 1.0 0.5 0.0 alkoxy silyl group and/or the silanol grouprelative to combined mass of (A) and (B) Evaluation Rupture elongationStretching 1000 1000 1000 900 1000 1000 600 1000 1000 1200 1200 resultsconditions Pencil hardness — B B B 2B B 2B B 2B 3B 4B 4B Waterresistance — ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ X X Chemical resistance — ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯◯ X X Scratch resistance A ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Δ Δ B ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ X X

Working Example 10

In a simple pressure reaction apparatus equipped with a stirrer andheater, 184.7 parts of a polycarbonate diol with an Mn of 900 resultingfrom a reaction between a mixture of 1,4-cyclohexanedimethanol and1,6-hexanediol (molar ratio 50:50) and ethylene carbonate as (a1), 68.4parts of a polycarbonate diol with an Mn of 2,000 resulting from areaction between 1,6-hexanediol and ethylene carbonate as (a2), 29 partsof DMPA as (a3), 26.9 parts of 1,6-hexanediol as (a4), 178.2 parts ofhydrogenated MDI as (B) and 487.3 parts of methyl ethyl ketone as areaction solvent were placed and stirred at 90° C. for 24 hours, leadingto a urethanation reaction, with a methyl ethyl ketone solution of apolyurethane resin obtained as a result. With 25.5 parts of 3-glycidoxypropyl trimethoxysilane added as a compound (X), a 10-minute stirringwas provided at 30° C., with 1,000 parts of a methyl ethyl ketonesolution containing a polyurethane resin (U2-6) containing a carboxylgroup in each molecule and 3-glycidoxy propyl trimethoxysilane obtainedas a result. A multilayer film for decorative molding was then obtainedusing the same method as working example 1, except that a methyl ethylketone solution containing a polyurethane resin (U2-6) containing acarboxyl group in each molecule and 3-glycidoxy propyl trimethoxysilanewas used.

Working Example 11

A multilayer film for decorative molding was obtained using the samemethod as working example 2, except that the methyl ethyl ketonesolution containing a polyurethane resin (U2-6) containing a carboxylgroup in each molecule and 3-glycidoxy propyl trimethoxysilane asobtained in working example 10 was used.

Working Example 12

A multilayer film for decorative molding was obtained using the samemethod as working example 3, except that the methyl ethyl ketonesolution containing a polyurethane resin (U2-6) containing a carboxylgroup in each molecule and 3-glycidoxy propyl trimethoxysilane asobtained in working example 10 was used.

Working Examples 13 to 22

A methyl ethyl ketone solution containing one of the polyurethane resins(U2-7) to (U2-16) having a carboxyl group in each molecule and3-glycidoxy propyl trimethoxysilane or 3-glycidoxy propyl methyldimethoxy silane was obtained in the same manner as working example 8,except that the types and amounts used of the input materials werechanged to those specified in Table 2. A multilayer film for decorativemolding was then obtained using the same method as working example 1,except that a methyl ethyl ketone solution containing one of thepolyurethane resins (U2-7) to (U2-16) having a carboxyl group in eachmolecule and 3-glycidoxy propyl trimethoxysilane or 3-glycidoxy propylmethyl dimethoxy silane was used.

Working Example 23

In a simple pressure reaction apparatus equipped with a stirrer andheater, 280.8 parts of a polycarbonate diol with an Mn of 900 resultingfrom a reaction between a mixture of 1,4-cyclohexanedimethanol and1,6-hexanediol (molar ratio 50:50) and ethylene carbonate as (a1), 21.5parts of ethylene glycol as (a4), 26.9 parts of 1,6-hexanediol also as(a4), 138.4 parts of hydrogenated MD as (B), 29.6 parts of HDI also as(B) and 470.5 parts of methyl ethyl ketone as a reaction solvent wereplaced and stirred at 90° C. for 24 hours, leading to a urethanationreaction, with a methyl ethyl ketone solution of a polyurethane resinhaving a terminal isocyanate group obtained as a result. Next, 11.2parts of a monoamine having a ketimine bond resulting from a reactionbetween diethylene triamine and methyl isobutyl ketone as (a5) was fedand stirred at 60° C. for 30 minutes, and, after feeding 28.2 parts ofwater, a 10-minute stirring was provided at 60° C., with a polyurethaneresin having a terminal amino group obtained as a result. With 19.8parts of 3-glycidoxy propyl trimethoxysilane added at 30° C., a10-minute stirring was provided, with a methyl ethyl ketone solutioncontaining a polyurethane resin (U1-3) having a silanol group in eachmolecule obtained as a result. A multilayer film for decorative moldingwas then obtained using the same method as working example 1, exceptthat a polyurethane resin (U1-3) having a silanol group in each moleculewas used.

Comparative Example 3

A methyl ethyl ketone solution containing a polyurethane resin (U2′-3)having a carboxyl group in each molecule and 3-glycidoxy propyltrimethoxysilane was obtained in the same manner as working example 8,except that the types and amounts used of the input materials werechanged to those specified in Table 2. A multilayer film for decorativemolding was then obtained using the same method as working example 1,except that a methyl ethyl ketone solution containing a polyurethaneresin (U2′-3) having a carboxyl group in each molecule and 3-glycidoxypropyl trimethoxysilane was used.

Comparative Example 4

A methyl ethyl ketone solution containing a polyurethane resin (U2′-4)having a carboxyl group in each molecule was obtained in the same manneras working example 8, except that the types and amounts used of theinput materials were changed to those specified in Table 2 and that acompound (X) was not added. A multilayer film for decorative molding wasthen obtained using the same method as working example 1, except that apolyurethane resin (U2′-4) was used.

Comparative Example 5

In a simple pressure reaction apparatus equipped with a stirrer andheater, 8.0 parts of ethylene glycol as (a4), 238.1 parts of a 3-mole POadduct of bisphenol A also as (a4), 23.4 parts of DMPA as (a3), 220.3parts of MDI as (B) and 489.6 parts of methyl ethyl ketone as a reactionsolvent were placed and stirred at 80° C. for 12 hours, leading to aurethanation reaction, with a methyl ethyl ketone solution of apolyurethane resin obtained as a result. With 20.6 parts of 3-glycidoxypropyl trimethoxysilane as a compound (X) added at 30° C., a 10-minutesstirring was provided, and 1,000 parts of a methyl ethyl ketone solutioncontaining a polyurethane resin (U2′-5) having a carboxyl group in eachmolecule and 3-glycidoxy propyl trimethoxysilane was obtained as aresult. A multilayer film for decorative molding was then obtained usingthe same method as working example 1, except that the polyurethane resin(U2′-5) was used.

TABLE 2 Working Working Working Working Working Working Working WorkingWorking example example example example example 10 example 11 example 12example 13 example 14 15 16 17 18 Type of polyurethane resin (U) U2-6U2-6 U2-6 U2-7 U2-8 U2-9 U2-10 U2-11 U2-12 Active (a1) A polycarbonatediol with an Mn of 1,000 resulting from a parts by — — — — — 115.4 — —83.1 hydrogen reaction between 1,4-cyclohexanedimethanol and an ethylenemass component carbonate (A) A polycarbonate diol with an Mn of 900resulting from a parts by 184.7 184.7 184.7 185.9 198.2 — 198.4 269.8 —reaction between a mixture of 1,4-cyclohexanedimethanol and mass1,6-hexanediol (molar ratio 50:50) and ethylene carbonate (a2) Apolycarbonate diol with an Mn of 2,000 resulting from a parts by — — — —— — — — 302.0 reaction between a mixture of 1,4-butanediol and1,6-hexanediol mass (molar ratio 70:30) and an ethylene carbonate Apolycarbonate diol with an Mn of 2,000 resulting from a parts by — — — —— — — 82.6 — reaction between a mixture of 1,3-propanediol and 1,4- massbutanediol (molar ratio 50:50) and ethylene carbonate A polycarbonatediol with an Mn of 1,000 resulting from a parts by — — — 67.4 71.9 — — —— reaction between a mixture of 1,4-butanediol and 1,6-hexanediol mass(molar ratio 70:30) and ethylene carbonate A polycarbonate diol with anMn of 2,000 resulting from a parts by 68.4 68.4 68.4 — — — — — —reaction between 1,6-hexanediol and ethylene carbonate mass (a3) DMPAparts by 29.0 29.0 29.0 52.5 23.4 34.0 52.5 14.6 14.6 mass (a4) Ethyleneglycol parts by — — — 2.53 14.9 44.9 20.5 3.96 — mass 1,3-propyleneglycol parts by — — — — — — — — — mass 1,6-hexanediol parts by 26.9 26.926.9 — — — — — — mass 3-mole PO adduct of bisphenol A parts by — — — — —— — — — mass (a5) A monoamine having a ketimine bond resulting from areaction parts by — — — — — — — — — between diethylene triamine andmethyl isobutyl ketone mass Organic IPDI parts by — — — — — — — 32.8 —polyisocyanate mass component (B) MDI-H parts by 178.2 178.2 178.2 180.9181.0 280.7 179.9 77.5 89.1 mass HDI parts by — — — — — — 38.5 8.3 —mass MDI parts by — — — — — — — — — mass Reaction solvent Methyl ethylketone parts by 487.3 487.3 487.3 490.1 490.1 475 489.7 489.7 490.6 massCompound (X) 3-glycidoxy propyl trimethoxysilane parts by 25.5 25.5 25.520.6 20.6 50.0 20.6 20.6 20.6 mass 3-glycidoxy propyl methyl dimethoxysilane parts by — — — — — — — — — mass Compound (Y)3-aminopropyltrimethoxysilane parts by — — — — — — — — — mass PropertiesMass fraction of the alicyclic hydrocarbon group contained in (a1) mass% 11.2 11.2 11.2 10.2 10.9 14.5 10.9 14.8 10.1 relative to combined massof (A) and (B) Total content of the carboxyl group and a salt thereofattributed to (a3) mmol/g 0.45 0.45 0.45 0.80 0.36 0.53 0.80 0.22 0.22present in (U) Combined concentration of the urethane groups and ureagroups present mmol/g 2.8 2.8 2.8 2.8 2.8 4.5 3.7 2.0 1.3 in (U) Massfraction of Si atoms attributed to the alkoxy silyl group and/or themass % 0.6 0.6 0.6 0.5 0.5 1.2 0.5 0.5 0.5 silanol group relative tocombined mass of (A) and (B) Evaluation Rupture elongation Stretching800 800 800 950 900 500 700 900 1200 results conditions Pencil hardness— B B B B B HB B 2B 3B Water resistance — ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ Chemicalresistance — ⊚ ⊚ ⊚ ◯ ⊚ ⊚ ◯ ◯ ◯ Scratch resistance A ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ B◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Working Working Working Working Working ComparativeComparative Comparative example 19 example 20 example 21 example 22example 23 example 3 example 4 example 5 Type of polyurethane resin (U)U2-13 U2-14 U2-15 U2-16 U1-3 U2′-3 U2′-4 U2′-5 Active (a1) Apolycarbonate diol with an Mn of 1,000 resulting from a parts by — — — —— — — — hydrogen reaction between 1,4-cyclohexanedimethanol and anethylene mass component carbonate (A) A polycarbonate diol with an Mn of900 resulting from a parts by 316.2 182.4 158.4 198.5 280.8 — 189.6 —reaction between a mixture of 1,4-cyclohexanedimethanol and mass1,6-hexanediol (molar ratio 50:50) and ethylene carbonate (a2) Apolycarbonate diol with an Mn of 2,000 resulting from a parts by — —105.6 — — — — — reaction between a mixture of 1,4-butanediol and1,6-hexanediol mass (molar ratio 70:30) and an ethylene carbonate Apolycarbonate diol with an Mn of 2,000 resulting from a parts by — 78.2— — — — — — reaction between a mixture of 1,3-propanediol and 1,4- massbutanediol (molar ratio 50:50) and ethylene carbonate A polycarbonatediol with an Mn of 1,000 resulting from a parts by — — — 72.0 — — — —reaction between a mixture of 1,4-butanediol and 1,6-hexanediol mass(molar ratio 70:30) and ethylene carbonate A polycarbonate diol with anMn of 2,000 resulting from a parts by — — — — — 239.0 — — reactionbetween 1,6-hexanediol and ethylene carbonate mass (a3) DMPA parts by11.7 51.5 29.5 23.4 — 29.0 29.8 23.4 mass (a4) Ethylene glycol parts by— 7.35 17.8 15.0 21.5 — — 8.0 mass 1,3-propylene glycol parts by 17.3 —— — — — — — mass 1,6-hexanediol parts by — — — — — 41.0 27.6 — mass3-mole PO adduct of bisphenol A parts by — — — — — — — 238.1 mass (a5) Amonoamine having a ketimine bond resulting from a reaction parts by — —— — 11.2 — — — between diethylene triamine and methyl isobutyl ketonemass Organic IPDI parts by — 160.4 — — — — — — polyisocyanate masscomponent (B) MDI-H parts by 119.1 — 184.5 181.2 138.4 178.2 182.9 —mass HDI parts by 25.5 — — — 29.6 — — — mass MDI parts by — — — — — — —220.3 mass Reaction solvent Methyl ethyl ketone parts by 489.7 479.8495.8 490.7 470.5 487.3 570.0 489.6 mass Compound (X) 3-glycidoxy propyltrimethoxysilane parts by 20.6 40.4 8.3 — 19.8 25.5 — 20.6 mass3-glycidoxy propyl methyl dimethoxy silane parts by — — — 19.2 — — — —mass Compound (Y) 3-aminopropyltrimethoxysilane parts by — — — — — — — —mass Properties Mass fraction of the alicyclic hydrocarbon groupcontained in (a1) mass % 17.4 10.2 19.1 10.9 16.1 0.0 11.2 0.0 relativeto combined mass of (A) and (B) Total content of the carboxyl group anda salt thereof attributed to (a3) mmol/g 0.18 0.80 0.45 0.36 0.00 0.450.51 0.36 present in (U) Combined concentration of the urethane groupsand urea groups mmol/g 2.5 3.0 2.8 2.8 2.8 2.8 3.2 3.6 present in (U)Mass fraction of Si atoms attributed to the alkoxy silyl group and/ormass % 0.5 1.0 0.2 0.5 0.5 0.6 0 0.5 the silanol group relative tocombined mass of (A) and (B) Evaluation Rupture elongation Stretching800 900 900 900 1200 1500 1500 300 results conditions Pencil hardness —2B 2B 2B B 2B 4B 4B H Water resistance — ⊚ ⊚ ⊚ ⊚ ⊚ Δ Δ Δ Chemicalresistance — ⊚ ◯ ⊚ ⊚ ⊚ Δ Δ Δ Scratch resistance A ◯ ◯ ◯ ◯ ◯ Δ Δ ◯ B ◯ ◯◯ ◯ ◯ X X ◯

Water dispersions or solvent solutions of polyurethane resins orpolyurethane resin compositions obtained under working examples 1 to 23and comparative examples 1 to 5 were subjected to measurements orevaluations of rupture elongation, pencil hardness, water resistance andchemical resistance using the methods described below. Further,decorative molded bodies were prepared and evaluated for the scratchresistance of an area ratio 0% molded product and that of an area ratio150% molded product using the methods described below. The results areshown in Tables 1 and 2.

Rupture Elongation Measurement Method

A molding film (a dry laminate of a 100 μm-thick unstretchedpolyethylene terephthalate film (manufactured by Toray Industries, Inc.,FL10), coated with a urethane-based adhesive (TR-7233, manufactured byShin-Nakamura Chemical Co., Ltd.) to a post-drying thickness of 0.5 μmusing a bar coater, and a 40 μm-thick unstretched polypropylene film(manufactured by Mitsui Chemicals Tohcello Inc., SC)) was coated withthe sample to a thickness equivalent to a post-drying thickness of 40 μmusing an applicator and dried at 80° C. for 10 minutes, and a dried filmof a polyurethane resin or polyurethane resin composition was obtainedas a result. After being peeled from the molding film, the dried film ofa polyurethane resin or polyurethane resin composition was cut into apiece 10 mm wide and 50 min long for use as a test specimen, which wasthen set on a tensile tester (manufactured by Shimazu, 100kNG) in such amanner that the tensile chucks are 20 mm apart and subjected to atensile test at a tension speed of 200 mm/min. More specifically, thetensile test took place in a thermostatic oven set to a temperature of100° C. after preheating the specimen for 60 seconds therein, and thepercentage elongation (%) of the specimen at the rupture point wasmeasured. The larger the rupture elongation, the more a film excels inmold-conformability when used as the protective layer of a multilayerfilm for decorative molding.

Pencil Hardness Measurement Method

A molding film (a dry laminate of a 100 μm-thick unstretchedpolyethylene terephthalate film (manufactured by Toray Industries, Inc.,FL10), coated with a urethane-based adhesive (TR-7233, manufactured byShin-Nakamura Chemical Co., Ltd.) to a post-drying thickness of 0.5 μmusing a bar coater, and a 40 μm-thick unstretched polypropylene film(manufactured by Mitsui Chemicals Tohcello Inc., SC)) was coated withthe sample to a thickness equivalent to a post-drying thickness of 40 μmusing an applicator and dried at 90° C. for 10 minutes, and a dried filmof a polyurethane resin or polyurethane resin composition was obtainedas a result. In accordance with JIS K 5600: 2008, a pencil was setagainst the dried film surface at a 45° angle and moved about 5 mm undera 750 g downward load to scratch it, and pencil hardness was determinedas the hardness of the pencil with the highest level of hardness thatdid not leave a scratch mark. The results are shown in Table 1. Thehigher the pencil hardness, the more a film excels in scratch resistancewhen used as the protective layer of a multilayer film for decorativemolding.

Water Resistance Evaluation Method

A steel plate was coated with the sample to a thickness equivalent to apost-drying thickness of 40 μm using an applicator and dried at 90° C.for 10 minutes, and a test specimen having a side covered with a driedfilm of a polyurethane resin or polyurethane resin composition wasobtained as a result. A drop of deionized water was then applied to thedried film surface, and the application site was covered with a 5 cmdiameter petri dish to prevent the drop from evaporating. After the testpiece was left to stand at 25° C. for 24 hours, the drop was removed byabsorbing it with cloth, and the appearance of the dried film wasevaluated by visual observation using the criteria below. The lesschange in appearance the dried film exhibits after the test, the morethe dried film excels in water resistance when used as the protectivelayer of a multilayer film for decorative molding.

⊚: No change◯: Becomes slightly opaqueΔ: Becomes considerably opaquex: The film peeling off the steel plate

Chemical Resistance Evaluation Method

A steel plate was coated with the sample to a thickness equivalent to apost-drying thickness of 40 μm using an applicator and dried at 90° C.for 10 minutes, and a test specimen having a side covered with a driedfilm of a polyurethane resin or polyurethane resin composition wasobtained as a result. A drop of an aqueous solution of 0.1N sodiumhydroxide was then applied to the dried film surface, and theapplication site was covered with a 5 cm diameter petri dish to preventthe drop from evaporating. After the test piece was left to stand at 25°C. for 24 hours, the drop was removed by absorbing it with cloth, andthe appearance of the dried film was evaluated by visual observationusing the criteria below. The less change in appearance the dried filmexhibits after the test, the more the dried film excels in chemicalresistance when used as the protective layer of a multilayer film fordecorative molding.

⊚: No change◯: Appears slightly markedΔ: Appears visibly markedx: The steel plate exposed

Scratch Resistance

A decorative molded body was prepared by setting a multilayer film fordecorative molding on the decorable object in such a manner that theadhesive layer-side of the film faces the largest face of the object andthen molding it using a TOM molding machine (manufactured by Fu-seVacuum Forming, Ltd., NGF0406-T) under the following conditions:

Molding temperature: 110° C.Heater output: During rapid heating 200%, during normal heating 80%Duration of rapid heating: 10 secondsVacuum pressure: 0 kPaCompressed air pressure: 300 kPaCompressed air supply duration: 15 secondsFlash time of atomospheric release: 0 seconds (during 0% molding in arearatio), 2 seconds (during 150% molding in area ratio)

Two draw ratio conditions, condition A and condition B, were implementedfor the decorating film by adjusting the depth of the box-shaped recessof the TOM molding machine. More specifically, conditions A and B were15 mm and 85 mm, respectively, in terms of the distance from theposition of the set film to the floor of the box-shaped recess. As thedecorable object, a plate-shaped resin molding measuring 250 mm long×100mm wide×3 mm thick, made of a polyolefin resin (TSOP GP6BS, manufacturedby Prime Polymer Co., Ltd.), was used.

After peeling the molding film from the obtained decorative molded body,the protective layer-side scratch resistance of the decorative moldedbody was evaluated in accordance with JIS K 5600-5-5: 2008. With workingexamples 2, 3, 11 and 12, however, the protective layer-side scratchresistance of the decorative molded body was evaluated without peelingthe molding film. More specifically, evaluations took place under thefollowing conditions:

Equipment: HEIDON 14-DR (manufactured by HEIDON)Scratch needle: Sapphire needle with 1 mm R-processed tip

Load: 200 g

Speed: 10 mm/seconds

Based on a visual observation of the condition of the surface, anevaluation was made against these judgment criteria: No scratch mark onthe protective layer ⊚, A scratch mark on the protective layer only ∘,The protective layer penetrated only, exposing the color layer, adhesivelayer or molding film (working examples 2, 3, 11 and 12 only) Δ, Theprotective layer, color layer, adhesive layer and molding film (workingexamples 2, 3, 11 and 12 only) completely penetrated, exposing thedecorable object x. Samples evaluated as ⊚ or ∘ were judged to be goodin scratch resistance, while those evaluated as Δ or x were judged to beunsatisfactory in scratch resistance. Each sample was measured threetimes, and, when measurement results differed, the worst one was adoptedas the evaluation result.

INDUSTRIAL APPLICABILITY

The multilayer film for decorative can be advantageously used whendecorating automobile parts and electrical appliances, but applicationsare not limited thereto. Namely, it can also be advantageously appliedto other fields, such as IT equipment, including mobile phones, notebookcomputers and the like, where, as well as scratch resistance, durabilityand other functionalities, esthetic design characteristics are required.

1.-19. (canceled)
 20. A multilayer film for decorative molding having amultilayer structure comprising a protective layer, a color layer and anadhesive layer arranged in this order, with a molding film disposedbetween either of the adjoining pairs of layers or on an oppositesurface of the protective layer to the color layer, wherein theprotective layer contains a polyurethane resin (U) formed at least froman active hydrogen component (A) and an organic isocyanate component (B)and having a polycarbonate skeleton with an alicyclic hydrocarbon groupand that condition (1) and/or condition (2) are satisfied: (1): Thepolyurethane resin (U) is a polyurethane resin (U1) that has analkoxysilyl group and/or a silanol group in a molecule, (2): Theprotective layer contains a compound (X) that has a glycidyl ethergroup, and an alkoxysilyl group and/or a silanol group, and thepolyurethane resin (U) is a polyurethane resin (U2) that has an aminogroup, or a carboxyl group and/or a salt thereof.
 21. The film asdescribed in claim 20, wherein the active hydrogen component (A)contains a polycarbonate polyol (a1) having an alicyclic hydrocarbongroup.
 22. The film as described in claim 21, wherein number averagemolecular weight of the polycarbonate polyol (a1) is 500 to 5,000 andmass fraction of the alicyclic hydrocarbon group contained in thepolycarbonate polyol (a1) is 1 to 30 mass % relative to the combinedmass of the active hydrogen component (A) and the organic isocyanatecomponent (B).
 23. The film as described in claim 20, wherein thecombined mass fraction of the Si atoms attributed to the alkoxy silylgroup and/or the silanol group contained in the polyurethane resin (U)and the Si atoms attributed to the alkoxy silyl group and/or the silanolgroup contained in the compound (X) is 0.05 to 2.0 mass % relative tothe combined mass of the active hydrogen component (A) and the organicisocyanate component (B).
 24. The film as described in claim 20, whereinthe organic isocyanate component (B) comprises an alicyclicpolyisocyanate (b1) with a carbon number of 6 to 18 and/or an aliphaticpolyisocyanate (b2) with a carbon number of 4 to
 22. 25. The film asdescribed in claim 20, wherein the organic isocyanate component (B)comprises isophorone diisocyanate and/or 4,4-dicyclohexyl methanediisocyanate.
 26. A polyurethane resin for a multilayer film fordecorative molding formed at least from an active hydrogen component (A)and an organic isocyanate component (B), having a polycarbonate skeletonwith an alicyclic hydrocarbon group, and having an alkoxy silyl groupand/or a silanol group.
 27. The polyurethane resin as described in claim26, wherein the active hydrogen component (A) contains a polycarbonatepolyol (a1) having an alicyclic hydrocarbon group.
 28. The polyurethaneresin as described in claim 27, wherein number average molecular weightof the polycarbonate polyol (a1) is 500 to 5,000 and mass fraction ofthe alicyclic hydrocarbon group contained in the polycarbonate polyol(a1) is 1 to 30 mass % relative to the combined mass of the activehydrogen component (A) and the organic isocyanate component (B).
 29. Thepolyurethane resin as described in claim 26, wherein the mass fractionof the Si atoms attributed to the alkoxy silyl group and/or the silanolgroup contained in a polyurethane resin (U1) is 0.05 to 2.0 mass %relative to the combined mass of the active hydrogen component (A) andthe organic isocyanate component (B).
 30. The polyurethane resin asdescribed in claim 26, wherein the organic isocyanate component (B)comprises an alicyclic polyisocyanate (b1) with a carbon number of 6 to18 and/or an aliphatic polyisocyanate (b2) with a carbon number of 4 to22.
 31. The polyurethane resin as described in claim 26, wherein theorganic isocyanate component (B) comprises isophorone diisocyanateand/or 4,4-dicyclohexyl methane diisocyanate.
 32. A polyurethane resincomposition for a multilayer film for decorative molding, formed atleast from an active hydrogen component (A) and an organic isocyanatecomponent (B), having a polycarbonate skeleton with an alicyclichydrocarbon group, containing a polyurethane resin (U2) having an aminogroup, or a carboxyl group and/or a salt thereof, and containing acompound (X) having a glycidyl ether group, and an alkoxy silyl groupand/or a silanol group.
 33. The polyurethane resin composition asdescribed in claim 32, wherein the active hydrogen component (A)contains a polycarbonate polyol (a1) having an alicyclic hydrocarbongroup.
 34. The polyurethane resin composition as described in claim 33,wherein number average molecular weight of the polycarbonate polyol (a1)is 500 to 5,000 and mass fraction of the alicyclic hydrocarbon groupcontained in the polycarbonate polyol (a1) is 1 to 30 mass % relative tothe combined mass of the active hydrogen component (A) and the organicisocyanate component (B).
 35. The polyurethane resin composition asdescribed in claim 32, wherein the mass fraction of the Si atomsattributed to the alkoxy silyl group and/or the silanol group containedin the compound (X) is 0.05 to 2.0 mass % relative to the combined massof the active hydrogen component (A) and the organic isocyanatecomponent (B).
 36. The polyurethane resin composition as described inclaim 32, wherein the organic isocyanate component (B) comprises analicyclic polyisocyanate (b1) with a carbon number of 6 to 18 and/or analiphatic polyisocyanate (b2) with a carbon number of 4 to
 22. 37. Thepolyurethane resin composition as described in claim 32, wherein theorganic isocyanate component (B) comprises isophorone diisocyanateand/or 4,4-dicyclohexyl methane diisocyanate.
 38. A method of producinga decorative molded body comprising bonding a multilayer film fordecorative molding onto a decorable object, wherein the multilayer filmfor decorative molding has a multilayer structure comprising aprotective layer, a color layer and an adhesive layer arranged in thisorder, with a molding film disposed between either of the adjoiningpairs of layers or on the opposite surface of the protective layer tothe color layer, that the protective layer contains a polyurethane resin(U) formed at least from an active hydrogen component (A) and an organicisocyanate component (B) and has a polycarbonate skeleton with analicyclic hydrocarbon group, and that condition (1) and/or condition (2)are satisfied: (1): The polyurethane resin (U) has an alkoxysilyl groupand/or a silanol group in a molecule, (2): The protective layer containsa compound (X) that has a glycidyl ether group, and an alkoxysilyl groupand/or a silanol group, and the polyurethane resin (U) has a carboxylgroup and/or a salt thereof.